Steam treatment of sulfur-containing heavy crude oil or oil residu with a combination catalyst comprising a hydrogenation-desulfurization catalyst and an overbased jet fuel containing an alkaline earth or alkali metal alkyl phenol complex

ABSTRACT

AN OVERBASED JET FUEL CONTAINING DISPERSED ALKALINE EARTH METAL CARBONATE, E.G., CALCIUM CARBONATE, AND AN ALKALINE EARTH OR ALKALI METAL ALKYL PHEONOL COMPLEX, E.G., CALCIUM OCTYL PHENOL COMPLEX, IS COMBINED WITH AN OIL SOLUBLE HYDROGENATION AND DESULFURIZATION CATALYST, E.G., NICKEL STEARATE, TO PROVIDE A CATALYST FOR A HIGH TEMPERATURE, ELEVATD PRESSURE STEAM TREATMET OF A HEAVY CRUDE OIL OR OIL RESIDUE TO GENERATE IN SITU HYDROGEN THUS REDUCING THE SPECIFIC GRAVITY AND THE SULFUR CONTENT OF THE CRUDE AND MINIMIZING COKE FORMATION.

United States Patent 3,649,527 STEAM TREATMENT OF SULFUR-CONTAINING HEAVY CRUDE OIL OR 01L RESIDUE WITH A COMBINATION CATALYST COMPRISING A HY- DROGENATION-DESULFURIZATION CATALYST AND AN OVERBASED JET FUEL CONTAINING AN ALKALINE EARTH 0R ALKALI METAL ALKYL PHENOL COMPLEX Armin C. Pitchford and Albert N. de Vault, Bartlesville, Okla, assignors to Phillips Petroleum Company No Drawing. Filed Mar. 23, 1970, Ser. No. 22,098 Int. Cl. C10g 23/02 US. Cl. 208-217 5 Claims ABSTRACT OF THE DISCLOSURE An overbased jet fuel containing dispersed alkaline earth metal carbonate, e.g., calcium carbonate, and an alkaline earth or alkali metal alkyl phenol complex, e.g., calcium octyl phenol complex, is combined with an oil soluble hydrogenation and desulfurization catalyst, e.g., nickel stearate, to provide a catalyst for a high temperature, elevated pressure steam treatment of a heavy crude oil or oil residue to generate in situ hydrogen thus reducing the specific gravity and the sulfur content of the crude and minimizing coke formation.

This invention relates to the treatment of sulfur-containing heavy crude oil or oil residue. In one of its aspects the invention relates to the steam treatment of such oils with a hydrogenation-desulfurization catalyst and and overbased jet fuel containing an alkaline earth metal alkyl phenol complex.

According to a concept of the present invention, there is provided a steam conversion of a residual oil product or a heavy crude oil with a combination catalyst system composed of a hydrogenation-desulfurization catalyst and an overbased jet fuel containing an alkaline earth or alkali metal alklyl phenol complex.

The steam reforming of various hydrocarbons is known. In such operation there is generally encountered during the reforming reaction a tendency of the heated heavy hydrocarbon to crack or decompose with the resultant formation of carbon. Also, in the reforming of such hydrocarbons, it is highly desirable to reduce sulfur content by in situ generating hydrogen.

We have now discovered that water-gas activity in the high temperature steam treatment of oils as herein set out can be provided by the use of an overbased jet fuel containing colloidally dispersed calcium carbonate and a calcium octyl phenol complex.

It is an object of this invention to treat with steam a heavy crude oil or oil residue. It is another object of this invention to reduce the carbon formation during the high temperature steam treatment of a heavy oil. It is a further object of this invention to reduce the viscosity of a heavy oil during a high temperature steam treatment thereof. It is a further object of the invention to reduce the sulfur content of a heavy oil.

Other aspects, concepts and objects of the invention are apparent from a study of this disclosure and the appended claims.

According to the present invention a heavy oil is treated with steam at an elevated temperature and pressure by subjecting said oil and steam in a reaction zone to the action of a catalyst comprising an overbased jet fuel containing an alkaline earth or alkali metal alkyl phenol complex.

As an illustration of the invention, the following examples are submitted.

3,649,527 Patented Mar. 14, 1972 EXAMPLE I An overbased jet fuel was prepared by combining the following ingredients:

Octyl phenol (p-l,1,3,3,-tetramethylbutyl phenol) gms 200 Jet fuel ml 800 Calcium hydroxide gms Overbasing agent (70/30 water/C H OH) ml 32 After passing 16 liters of CO through the above mixture, water was removed by inert gas stripping at 200 F. for 23 hours using nitrogen as the inert gas. Excess lime was removed by filtration. By titration, the resulting product was found to contain 35 grams of Ca/liter.

EXAMPLE II The following homogeneous feedstock was prepared for a steam conversion test:

Grams Overbased jet fuel (from Example 1) 53.7 Nickel stearate 20.0 Eocene-Ratawi crude oil 926.3

The mixture was pumped through a tube reactor along with super heated steam. Water and liquid hydrocarbon products were collected in a separator and gaseous materials were sampled, metered and vented. The following test conditions were used:

Sulfur removal, percent Residence time was adjusted to provide a liquid hourly space velocity of one volume of feed including catalyst/ volume of reactor/hour. Steam was super heated to 950975 F. and charged through the lower portion of the vertical tube reactor to raise the temperature of the crude to the approximate operating temperature. Liquid water was pumped to the steam generator at the same rate as the crude oil in this test.

From the foregoing example it can be seen that the weight percent sulfur of the original crude which was 4.0 had been reduced in the primary separator product of 2.24; the carbon residue of the original crude which was 9.07 was reduced in the primary separator product to 2.69 and that the total product recovery, excluding coke and gases which amounted to cc./ml. feed, was 92.1 weight percent.

With reference to Example I, the temperature during the addition of carbon dioxide at atmospheric pressure is ordinarily in the range of from about 200 to about 300 F., provided there is sufiicient pressure to keep the jet fuel, water and phenol used in essentially liquid phase. The now preferred range at atmospheric pressure is from about 150 to about 165 F. It will be understood by one skilled in the art in possession of this disclosure that the conditions here given for overbasing the jet fuel to prepare the product of Example I is an operation in which the conditions can be varied. It is essential only to obtain the overbased jet fuel containing the dispersed, e.g., colloidally dispersed, calcium carbonate or its equivalent.

The proportion of the alkyl phenol, e.g., octyl phenol, to the jet fuel should be such that excessive thickening of the system upon introduction of carbon dioxide will not take place. At present, ratios of 1 alkyl phenol, e.g., octyl phenol, to 4 of jet fuel to 1 alkyl phenol, e.g., octyl phenol, to 5 of jet fuel are preferred.

In the overbasing agent, the water to phenol ratio should include mixtures comprising to 90 percent phenol. A 70 percent phonol solution is now preferred, this being a saturated solution at ambient temperature.

The alkaline earth metal hydroxide, e.g., calcium hydroxide, and the carbon dioxide can be varied according to the amount of dispersed alkaline earth metal, e.g., calcium, desired in the finished product.

The hydrogenation-desulfurization catalyst which can be used in addition to the nickel are, for example, cobalt and/or molybdenum, compounds, for example, the corresponding naphthenates, octanoates or stearate. These may be used as heterogeneous suspensions or slurries of conventional hydrogenation catalyst, either supported or unsupported, as may be best suited to the purposes of the operator.

The proportion of the hydrogenation-desulfurization catalyst in the crude oil can vary considerably, for example, the proportions now contemplated are from about 0.1 to about 10 percent based on the crude oil.

The reaction temperatures for treatment of the oil will usually range from about 600 to about 850 PI, a now preferred range being 675-840 F.

The pressure can vary. Usually a pressure of from about 250 to about 5,000 p.s.i.g. with a preferred pressure range of about 500 to about 2,500 p.s.i.g. will be used.

The water to crude oil ratio, i.e., the steam to crude oil, can vary from about 0.05 to about 10, now preferred range being from about 0.1 to about 5.

It is Within the scope of the invention to substitute for some or all of the jet fuel the crude oil to be treated with the steam and catalyst. Further, sulfonates such as overbased metal petroleum sulfonates can be substituted at least in part so long as sufficient alkaline earth or alkali metal is provided to promote water-gas reaction activity.

As alkaline earth or alkali metals for overbasing the jet fuel, there can be employed calcium, barium, magnesium, strontium, potassium and other metals of Group I-A and IIA metals.

The jet fuel used in the experimental work described in this disclosure was of the IP-S type which is a Navy kerosene based fuel JP-S which conforms to Military Specifications MILT-5624G. Boiling range of this prod uct is from about 335 A. to 540 F. It has an API Gravity of 36-48. Aromatic content was less than volume percent and the typical value of about 1215 percent of aromatics was observed. Olefin content did not exceed 5.0 volume percent.

These characteristics are now not believed to be critical since the jet fuel was simply used as a carrier for the alkyl phenol, e.g., octyl phenol, complex. Other hydrocarbons could have been used. Thus, hydrocarbons that can be used as a carrier for the alkyl phenol, e.g., octyl phenol, complex are C C hydrocarbons or mixtures including various distillate fractions of the crude oil. Examples of petroleum fractions that can be used are: petroleum ether, gasoline, naphtha, kerosene, fuel o l and gas oil.

Very little is actually known regarding the composition of the alkyl phenol complex. There can be various substituents on the alkyl phenol. For example, note the following:

wherein X is an alkyl and can contain 1-12 carbon atoms, Y can be hydrogen or a radical containing l-l2 carbon atoms and n is 1, 2 or 3.

The broad limits of X can vary from C to about C and Y can be hydrogen or a C to about C radical.

Examples of alkyl phenols are:

3-methylphenol 3'tert-butylphenol p-tert-amylphenol Z-hepylphenol 2,4-di(5-butylhexadecyl) phenol 3,5-di(4-ethyldecyl) phenol 3 ,4-dimethylphenol 4-octylphenol 3-nonylphenol 3-eicosylphenol 4-dodecylphenol 2,6-di-tert-butylphenol Z-tert-butyl-5-methylphenol Z-methyl-hydroquinone 4-isobutyl-resorcinol 2,S-di-tert-butyl-hydroquinone.

In fact, both X and Y can vary as long as the material is soluble in the hydrocarbon at the overbasing temperature which cannot exceed the boiling point of water at atmospheric pressure. Higher temperatures can be used in a pressurized system provided solubility of the particular alkyl phenol is achieved.

Other derivatives of phenols can be used.

Soluble nickel, cobalt, molybdenum, iron, hydrogenatiou-desulfurization catalysts can be employed. Generally, the corresponding salts of high molecular weight acids such as naphthenates, octoates, stearates, etc. are desirable and are now preferred over unsupported heterogeneous catalysts or slurries of these catalysts.

The proportions of the soluble catalyst mixed with the overbased jet fuel can vary greatly. Nickel stearate in Example II, for example, comprises 2 weight percent of the total overbased jet fuel-crude oil mixture. This percentage can vary as desired from about 0.1 to about 10 percent, and will be preferably 1-3 percent based on the total feed to the reactor. This is equivalent to 10 parts of Ni stearate/54 parts of overbased jet fuel (1 percent of total) to 30 parts of Ni stearate/54 parts of overbased jet fuel (3 percent of total).

In lieu of the C H OH of Example I other equivalent operative compounds can be used. It is now believed that the pH of the resulting 70/30 mixture may be the controlling factor and that the pH should range from about 4 to about 7. Those substituted phenols which will pro vide 4-7 pH are now considered suitable. Other equivalently operating materials can be used, e.g., an alcohol, such as methanol, but are not now preferred.

While the jet fuel may contribute some hydrogen to the reaction described in this invention, it is now believed that most of the hydrogen is supplied by the steam by way of the water-gas reaction:

Hydrogen exchange reactions may take place between the jet fuel and the crude or between the various crude Oll components.

The now preferred ranges for a steam conversion as exemplified in Example II are as follows:

Percent Overbased jet fuel 2-10 Ni stearate .5-5 Crude oil 85-975 Further, other hydrocarbons can be used as a carrier. These can include C -C hydrocarbons or mixtures, including various distillate fractions of the crude.

The catalyst employed in the invention operation is dispersed and/or soluble in the oil which is treated.

Reasonable variation and modification are possible within the scope of the foregoing disclosure and the appended claims to the invention the essence of which is that there have been combined a hydrogenation-desulfurization catalyst and an overbased jet fuel containing an alkaline earth or alkali metal alkyl phenol complex to provide a catalyst for the high temperature steam treatment of a heavy oil to convert the same to a product of lower specific gravity, lower carbon and sulfur contents.

We claim:

1. A process for the steam treatment of a sulfur containing heavy oil at an elevated temperature and pressure which comprises subjecting said oil in the presence of steam to the action of a catalyst comprising (1) a compound selected from naphthenates, octanoates, and stearates of nickel, and (2) an overbased jet fuel containing a dispersed alkali metal carbonate or alkaline earth metal carbonate and a metal alkyl phenol complex, said overbase jet fuel having been prepared by passing carbon di- 6 oxide gas through a mixture containing an alkyl phenol, an alkali metal hydroxide or alkaline earth metal hydroxide and a Water-phenol overbasing agent and then stripping water from the overbased reaction mixture thus obtained, and recovering an oil having a reduced viscosity and a lowered sulfur content.

2. A process according to claim 1 wherein the heavy oil is a heavy crude oil containing sulfur.

3. A process according to claim 1 wherein the oil is a heavy oil residue.

4. A process according to claim 1 wherein said overbased jet fuel contains dispersed calcium carbonate and calcium octyl phenol complex.

5. A process according to claim 4 wherein said compound is nickel stearate.

References Cited UNITED STATES PATENTS 2,697,682 12/ 1954 Porter 208-214 2,776,245 1/ 1957 Sowerwine, Ir. 208-217 FOREIGN PATENTS 248,362 3/1963 Australia 2O8214 DELBERT E. GANTZ, Primary Examiner G. J. CRASANAKIS, Assistant Examiner US. Cl. X.R. 208--226; 252431 

